JP7260247B2 - Compositions containing multi-stage polymers, methods for their preparation and uses thereof - Google Patents

Description

The present invention relates to polymer compositions comprising (meth)acrylic polymers and multi-stage polymers.

In particular, the present invention relates to polymer compositions comprising (meth)acrylic polymers and multi-stage polymers and which can be used as masterbatches.

More specifically, the present invention also relates to methods of preparing polymer compositions comprising (meth)acrylic polymers and multistage polymers by spray drying or coagulation.

[Technical problem]
Thermosetting polymers are most widely used as matrix materials in composites. Thermoset polymers are infusible and insoluble polymer networks. One possibility of obtaining thermoset polymers is by a curing reaction between a thermoset resin, such as an epoxy resin or a polyester resin, and a hardener or curing agent.

Due to the high crosslink density, the material has a high glass transition temperature, which gives the material excellent thermodynamic properties. However, the impact strength properties of thermoset polymers are unsatisfactory for many applications.

Rubber materials are usually added to increase the impact strength.

Such rubbers are in the form of core-shell particles and can be multistage polymers having at least one stage that is rubber.

Multi-stage polymers in the form of core-shell particles are available as agglomerated dry particles, which are dispersed in a matrix for uniform distribution. For some thermosetting resins, especially epoxy resins, it is very difficult or nearly impossible to properly disperse these multi-stage polymer particles.

Complex techniques also exist for incorporating multi-stage polymers in the form of core-shell particles into epoxy resins without drying the multi-stage polymers after their synthesis process by progressively changing the continuous dispersion medium of the core-shell particles from water to organic solvents. do.

It is an object of the present invention to obtain polymer compositions containing multistage polymers that can be readily dispersed in uncured resins such as epoxies, polyesters and (meth)acrylics.

It is also an object of the present invention to have an effective and uniform distribution of multistage polymers in resins such as epoxies, polyesters and (meth)acrylics.

Another object of the present invention is to avoid agglomeration of multistage polymer particles in resins such as epoxies, polyesters and (meth)acrylics.

An additional object of the present invention is to toughen thermoset or thermoplastic matrices of epoxy, polyester or (meth)acrylic resins with uniform distribution of impact modifiers in the form of multistage polymers. .

Yet another object of the invention is a method of making a polymer composition comprising a multi-stage polymer that can be readily dispersed in an uncured epoxy, polyester or (meth)acrylic resin.

A further object is to have a method of preparing a polymer composition comprising a multi-stage polymer that can be readily dispersed in an uncured epoxy, polyester or (meth)acrylic resin, and a corresponding thermosetting To have an effective and uniform distribution of the multi-stage polymer in the resin.

Yet another object is the use of polymer compositions containing multi-stage polymers that are masterbatches for impact modifying thermoset resins containing epoxy, polyester or (meth)acrylic resins.

Yet another object of the present invention is a (meth)polymer used as a masterbatch with a uniform distribution of multi-stage polymers for impact modification of thermoset epoxy, polyester or (meth)acrylic resins. A method of making a polymer composition in the form of a free-flowing dry powder comprising an acrylic polymer and a multi-stage polymer.

BACKGROUND OF THE INVENTION PRIOR ART Document EP 0 228 450 discloses rubber-modified epoxy compounds. The composition comprises an epoxy resin continuous phase and a discontinuous phase of rubber particles dispersed in the continuous phase. The rubber particles are grafted rubber particles. The rubber particles are dispersed in the epoxy phase by a mixing or shearing device.

Document EP 0 911 358 discloses the use of block copolymers as impact modifiers in epoxy resins. However, block copolymers are relatively expensive and it is preferred to disperse standard core-shell impact modifiers in epoxy resins.

Document FR2934866 (our AM2509) discloses the polymer preparation of certain core-shell polymers with a functional shell comprising hydrophilic monomers. Core-shell polymers are used as impact modifiers in thermoset polymers.

Document EP 1 632 533 discloses a method for producing improved epoxy resins. Epoxy resin compositions have rubber-like polymer particles dispersed in the composition by the method of contacting the particles with an organic medium in which the rubber particles are dispersed.

Document EP 1 666 519 discloses a method for producing rubbery polymer particles and a method for producing resin compositions containing them.

Document EP 2 123 711 discloses a thermosetting resin composition having rubber-like polymer particles dispersed in the composition, and a process for its production.

None of the prior art documents disclose the claimed compositions or methods of obtaining them.

[Brief description of the invention]
Surprisingly,
a) a (meth)acrylic polymer (P1), and b) a multi-stage polymer, wherein the multi-stage polymer constitutes at least 20% by weight of the polymer composition, in an epoxy, polyester or (meth)acrylic resin It was found to be easily dispersible.

Surprisingly,
for a polymer composition comprising an epoxy, polyester or (meth)acrylic resin, comprising a) a (meth)acrylic polymer (P1), and b) a multistage polymer, the multistage polymer constituting at least 20% by weight of the polymer composition. It has also been found that it can be used as a masterbatch of

Surprisingly,
a) mixing a (meth)acrylic polymer (P1) and a multistage polymer,
b) A method for producing a polymer composition comprising the step of recovering the mixture obtained in the previous step, wherein the (meth)acrylic polymer (P1) and the multistage polymer in step a) are in the form of a dispersion in the aqueous phase. A method has also been found which leads to a polymer composition which can be used as a masterbatch for epoxy, polyester or (meth)acrylic resins.

Surprisingly,
a) a (meth)acrylic polymer (P1), and b)
a) one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C,
b) one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C
and wherein the polymer obtained by the multi-stage process constitutes at least 20% by weight of the composition a) + b) is readily dispersed in epoxy, polyester or (meth)acrylic resins and can be used as a masterbatch for epoxy, polyester or (meth)acrylic resins.

An AFM image of Comparative Example 1 and an AFM image of Example 1 are shown.

According to a first aspect, the invention comprises:
(meth)acrylic polymer (P1); Constituent, polymer composition.

According to a second aspect, the invention comprises:
(Meth)acrylic polymer (P1), and a multi-stage polymer, wherein the multi-stage polymer is
a) one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C,
b) one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C
and wherein the multistage polymer constitutes at least 20%, preferably at least 30%, more preferably at least 40%, advantageously at least 50% by weight of the polymer composition.

In a third aspect, the invention provides
a) mixing a (meth)acrylic polymer (P1) and a multi-stage polymer;
b) producing a polymer composition comprising drying the mixture obtained in the previous step, wherein the (meth)acrylic polymer (P1) and the multi-stage polymer in step a) are in the form of a dispersion in the aqueous phase Regarding the method.

In a fourth aspect, the invention provides
(meth)acrylic polymer (P1); It relates to the use of such polymer compositions as masterbatches for epoxy, polyester or (meth)acrylic resins.

In a fifth aspect, the invention provides
a) mixing a (meth)acrylic polymer (P) and a multistage polymer,
b) recovering the mixture obtained in the previous step, wherein the (meth)acrylic polymer (P1) and the multi-stage polymer in step a) are in the form of a dispersion in the aqueous phase, epoxy, polyester or (meth) ) to a method of making a polymer composition for use as a masterbatch for acrylic resins.

In a sixth aspect, the invention provides
a) mixing a (meth)acrylic polymer (P1) and a multi-stage polymer;
b) recovering the mixture obtained in the previous step, wherein the (meth)acrylic polymer (P1) and the multistage polymer in step a) are in the form of a dispersion in the aqueous phase; It relates to a method of manufacturing.

The term "polymer powder" as used means a polymer containing powder particles in the at least 1 micrometer (μm) range obtained by agglomeration of a primary polymer containing particles in the nanometer range.

The term "primary particles" used means spherical polymers containing particles in the nanometer range. Preferably, the primary particles have a weight average particle size of 20nm-800nm.

The term "particle size" as used means the volume average diameter of particles that are considered spherical.

The term "copolymer" as used means a polymer consisting of at least two different monomers.

As used, "multi-stage polymer" means a polymer formed sequentially by a multi-stage polymerization process. the first polymer is the first stage polymer and the second polymer is the second stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer; A multi-stage emulsion polymerization process is preferred.

The term "(meth)acrylic" used means all kinds of acrylic and methacrylic monomers.

The term "(meth)acrylic polymer" used means that the (meth)acrylic polymer essentially comprises a polymer comprising (meth)acrylic monomers constituting 50% by weight or more of the (meth)acrylic polymer. means.

The term "epoxy resin" used is understood as any organic compound having at least two oxirane-type functional groups capable of polymerizing by ring opening.

The term "(meth)acrylic resins" used is understood as adhesives based on acrylic and methacrylic monomers.

The term "masterbatch" used is understood as a composition with a high concentration of additives in a carrier material. Additives are dispersed in the carrier material.

A multistage polymer according to the present invention has at least two stages that differ in their polymer composition.

The multistage polymer is preferably in the form of polymer particles, which are considered spherical particles. These particles are also called core-shell particles. The first stage forms the core and the second or all subsequent stages form the respective shells.

For spherical polymer particles, it has a weight average particle size of 20 nm-800 nm. Preferably the weight average particle size of the polymer is 25 nm-600 nm, more preferably 30 nm-550 nm, even more preferably 35 nm-500 nm, preferably 40 nm-400 nm, more preferably 50 nm-350 nm, most preferably 80 nm- 300 nm.

The polymer particles comprise at least one layer (A) comprising a polymer (A1) having a glass transition temperature below 0°C and another layer (B) comprising a polymer (B1) having a glass transition temperature above 60°C. It has a multi-layered structure, including Preferably, the polymer (B1) with a glass transition temperature of at least 30° C. is the outer layer of a polymer particle with a multilayer structure. Preferably, step (A) is the first step and step (B) comprising polymer (B1) is grafted onto step (A) comprising polymer (A1) or another intermediate layer.

Polymer particles are obtained by multi-stage processes, such as processes involving two, three or more stages.

A polymer (A1) with a glass transition temperature below 0° C. in layer (A) is never made during the last stage of a multi-stage process. This means that polymer (A1) is never in the outer layer of particles with a multilayer structure. The polymer (A1) with a glass transition temperature below 0° C. in layer (A) is in the core or one of the inner layers of the polymer particle.

Preferably, the polymer (A1) with a glass transition temperature below 0° C. in layer (A) is made in the first stage of a multi-stage process forming the core of polymer particles with a multilayer structure. Preferably polymer (A1) has a glass transition temperature below -5°C, more preferably below -15°C, advantageously below -25°C.

Preferably, the polymer (B1) with a glass transition temperature above 60° C. is made in the last stage of a multi-stage process forming the outer layer of polymer particles with a multilayer structure.

Additional intermediate layer(s) may be present, provided by intermediate stage(s).

The glass transition temperature Tg of each polymer can be evaluated by dynamic methods such as thermomechanical analysis.

In a first embodiment, for polymer (A1) it is a (meth)acrylic polymer comprising at least 50% by weight of alkyl acrylate-derived monomers.

More preferably, polymer (A1) comprises comonomer(s) that can be copolymerized with alkyl acrylates, as long as polymer (A1) has a glass transition temperature below 0°C.

The comonomer(s) in polymer (A1) are preferably selected from (meth)acrylic and/or vinyl monomers.

The (meth)acrylic comonomers in polymer (A1) comprise monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, the (meth)acrylic comonomers in polymer (A1) comprise C1-C4 alkyl methacrylate monomers and/or C1-C8 alkyl acrylate monomers.

Most preferably, the acrylic or methacrylic comonomers of polymer (A1) are methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert acrylate, as long as polymer (A1) has a glass transition temperature below 0°C. - butyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof.

Polymer (A1) is preferably crosslinked. This means that a crosslinker is added to the other monomer(s). A crosslinker contains at least two groups capable of polymerizing.

In one particular embodiment, polymer (A1) is a homopolymer of butyl acrylate.

In another particular embodiment, polymer (A1) is a copolymer of butyl acrylate and at least one crosslinker. The crosslinker is present at less than 5% by weight of the copolymer.

More preferably, the glass transition temperature Tg of polymer (A1) of the first embodiment is between -100°C and 0°C, even more preferably between -100°C and -5°C, advantageously between -90°C and -15°C. , more preferably between -90°C and -25°C.

In a second embodiment, polymer (A1) is a silicone rubber-based polymer. A silicone rubber is, for example, polydimethylsiloxane. More preferably, the glass transition temperature Tg of polymer (A1) of the second embodiment is between -150°C and 0°C, even more preferably between -145°C and -5°C, advantageously between -140°C and -15°C. , more preferably between -135°C and -25°C.

In a third embodiment, the polymer (A1) having a glass transition temperature of less than 0° C. comprises at least 50 wt. It is the inner layer. In other words, stage (A) comprising polymer (A1) is the core of the polymer particle.

By way of example, polymers (A1), which are the core of the second embodiment, include isoprene or butadiene homopolymers, isoprene-butadiene copolymers, copolymers of isoprene with up to 98% by weight of vinyl monomers, and up to 98% by weight of vinyl monomers. Copolymers of butadiene with weight percent vinyl monomers may be mentioned. Vinyl monomers may be styrene, alkyl styrenes, acrylonitrile, alkyl (meth)acrylates, or butadiene or isoprene. In one embodiment, the core is a butadiene homopolymer.

More preferably, the glass transition temperature Tg of the polymer (A1) of the third embodiment, comprising at least 50% by weight of polymer units derived from isoprene or butadiene, is between -100°C and 0°C, even more preferably -100°C. to -5°C, preferably -90°C to -15°C, even more preferably -90°C to -25°C.

As regards polymer (B1), mention may be made of homopolymers and copolymers containing monomers with double bonds and/or vinyl monomers. Preferably, polymer (B1) is a (meth)acrylic polymer.

Preferably, polymer (B1) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, polymer (B1) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and/or C1-C8 alkyl acrylate monomers.

Most preferably, the acrylic or methacrylic monomers of polymer (B1) are methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, as long as polymer (B1) has a glass transition temperature of at least 30°C. , butyl methacrylate and mixtures thereof.

Advantageously, polymer (B1) comprises at least 70% by weight of monomer units derived from methyl methacrylate.

Preferably, the glass transition temperature Tg of polymer (B1) is from 30°C to 150°C. The glass transition temperature of polymer (B1) is more preferably 50°C to 150°C, even more preferably 70°C to 150°C, preferably 90°C to 150°C, more preferably 90°C to 130°C.

With respect to the method of making a multi-stage polymer according to the present invention,
a) polymerizing by emulsion polymerization of a monomer or monomer mixture (A _m ) to obtain at least one layer (A) comprising a polymer (A1) having a glass transition temperature below 0° C.,
b) polymerizing by emulsion polymerization of a monomer or monomer mixture (B _m ) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30° C., wherein the monomer or monomer mixture (A _m ), and the monomer or monomer mixture (B _m ) are selected from the monomers according to the composition for polymer (A1) and polymer (B1) given above.

Preferably step a) is performed before step b). More preferably, if there are only two stages, step b) is carried out in the presence of polymer (A1) obtained in step a).

Advantageously, the method of making a multi-stage polymer composition according to the invention comprises:
a) polymerization by emulsion polymerization of a monomer or mixture of monomers (A _m ) to obtain a layer (A) comprising a polymer (A1) having a glass transition temperature below 0° C.,
b) polymerization by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C.

respective monomers or monomer mixtures (A m ) and (B _m ), and respective polymers (A1) and (B1), to form layers (A) and ( _B ), respectively, comprising polymers (A1) and (B1), respectively The properties of (B1) are the same as defined above.

The method of making a multi-stage polymer can include additional steps between steps a) and b) for additional stages.

The method of making a multi-stage polymer can also include additional steps for additional stages before steps a) and b). Seeds for polymerizing a monomer or monomer mixture (A _m ) by emulsion polymerization to obtain a layer (A) comprising a polymer (A1) having a glass transition temperature below 0° C. can be used. The seed is preferably a thermoplastic polymer with a glass transition temperature of at least 20°C.

A multi-stage polymer is obtained as an aqueous dispersion of polymer particles. The solids content of the dispersion is 10%-65% by weight.

As regards the (meth)acrylic polymer (P1), mention may be made of homopolymers and copolymers of (meth)acrylic monomers. Preferably, the (meth)acrylic polymer (P1) contains a (meth)acrylic monomer that constitutes 50% by weight or more of the (meth)acrylic polymer (P1). More preferably, the (meth)acrylic polymer (P1) comprises at least 60% by weight of (meth)acrylic monomers, advantageously at least 70% by weight.

Even more preferably, the (meth)acrylic polymer (P1) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Advantageously, the (meth)acrylic polymer (P1) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and/or C1-C8 alkyl acrylate monomers.

In one preferred embodiment, the (meth)acrylic polymer (P1) is 80 wt%-100 wt% methyl methacrylate, preferably 80 wt%-99.8 wt% methyl methacrylate and 0.2 wt% - Contains 20% by weight C1-C8 alkyl acrylate monomers. Advantageously, the C1-C8 alkyl acrylates are selected from methyl acrylate or butyl acrylate.

In one embodiment, the (meth)acrylic polymer (P1) also contains a functional comonomer.

The functional comonomer has the formula (1)

[wherein R ₁ is selected from H or CH ₃ and R ₂ is H or an aliphatic or aromatic group having at least one atom excluding C or H].

Preferably, the functional monomers are glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids such as dimethylacrylamide, 2-methoxyethyl acrylic acid or methacrylate, optionally tetra 2-aminoethyl acrylate or methacrylate, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkyl imidazolidinone (meth)acrylates, polyethylene glycol (meth)acrylates. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g/mol-10000 g/mol.

In a second preferred embodiment, the (meth)acrylic polymer (P1) comprises 0%-50% by weight of functional monomers. Preferably, the (meth)acrylic polymer (P1) is 0 wt%-30 wt% functional monomer, more preferably 1 wt%-30 wt%, even more preferably 2 wt%-30 wt%, advantageously 3%-30% by weight, more preferably 5%-30% by weight, most preferably 5%-30% by weight.

Preferably, the functional monomers of the second preferred embodiment are (meth)acrylic monomers. Functional monomers have the formula (2) or (3).

[wherein _in any of formulas (2) and (3) R ₁ is selected from H or CH ₃ ; is an aliphatic or aromatic group having at least one atom; in formula (3), Y is N and R ₄ and/or R ₃ are H or an aliphatic or aromatic group].

Preferably, functional monomers (2) or (3) are glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids such as dimethylacrylamide, 2-methoxy acrylic acid or methacrylate from ethyl, optionally quaternized 2-aminoethyl acrylate or methacrylate, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkyl imidazolidinone (meth)acrylates, polyethylene glycol (meth)acrylates selected. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g/mol-10000 g/mol.

Preferably, the glass transition temperature Tg of the (meth)acrylic polymer (P1) of all embodiments is from 30°C to 150°C. The glass transition temperature of the (meth)acrylic polymer (P1) is more preferably 40°C to 150°C, preferably 45°C to 150°C, more preferably 50°C to 150°C.

Preferably, the (meth)acrylic polymer (P1) of all embodiments is not crosslinked.

The (meth)acrylic polymer (P1) is preferably in the form of spherical polymer particles. The spherical polymer particles of (meth)acrylic polymer (P1) have a weight average particle size of 20 nm-800 nm. Preferably, the weight average particle size of the polymer is 30 nm-400 nm, more preferably 30 nm-350 nm, advantageously 35 nm-200 nm.

Preferably, the (meth)acrylic polymer (P1) of all embodiments is less than 100000 g/mol, preferably less than 90000 g/mol, more preferably less than 80000 g/mol, even more preferably less than 70000 g/mol, advantageously It has a weight-average molecular weight Mw of less than 60 000 g/mol.

Preferably, the (meth)acrylic polymer (P1) of all embodiments is above 2000 g/mol, preferably above 3000 g/mol, more preferably above 4000 g/mol, even more preferably above 5000 g/mol , preferably above 6000 g/mol, more preferably above 6500 g/mol, even more preferably above 7000 g/mol, most preferably above 10000 g/mol.

Advantageously, the weight average molecular weight Mw of the (meth)acrylic polymer (P1) of all embodiments is 2000 g/mol-100000 g/mol, preferably 3000 g/mol-90000 g/mol, more preferably 4000 g/mol-70000 g /mol, preferably 5000 g/mol-60000 g/mol, more preferably 7000 g/mol-60000 g/mol, most preferably 10000 g/mol-60000 g/mol.

Preferably, the polymer composition of the present invention comprising the (meth)acrylic polymer (P1) and the multi-stage polymer is solvent-free. Solvent-free means that the solvent finally present constitutes less than 1% by weight of the composition. Monomers in the synthesis of each polymer are not considered solvents. Residual monomers in the composition are present at less than 2% by weight of the composition.

Preferably, the polymer composition according to the invention is in a dry state. By dry state is meant that the polymer composition according to the invention contains less than 3% by weight of moisture, preferably less than 1.5% by weight of moisture, more preferably less than 1.2% by weight of moisture.

Moisture can be measured by a thermobalance, which heats the polymer composition and measures the weight loss.

The composition according to the invention, comprising a (meth)acrylic polymer (P1) and a multi-stage polymer, does not contain any optionally added solvent. Final residual monomers and water from the polymerization of each monomer are not considered solvents.

As regards the method of producing the (meth)acrylic polymer (P1) according to the invention, it comprises the step of polymerizing the respective (meth)acrylic monomer.

(Meth)acrylic homo- or copolymers (P1) can be made in a batch or semi-continuous process:
In a batch process, the mixture of monomers is introduced at once immediately before or immediately after the introduction of one or a portion of the initiator system,
In a semi-continuous process, the monomer mixture is added multiple times in parallel with the addition of the initiator (the initiator is also added multiple times or continuously) for a defined addition time that can range from 30-500 minutes. or added continuously.

With respect to the method of producing the polymer composition according to the invention,
a) mixing a (meth)acrylic polymer (P1) and a multistage polymer,
b) recovering the mixture obtained in the previous step in the form of polymer powder, the (meth)acrylic polymer (P1) and the multistage polymer in step a) being in the form of dispersion in the aqueous phase.

The amount of the aqueous dispersion of the (meth)acrylic polymer (P1) and the aqueous dispersion of the multi-stage polymer is such that the weight proportion of the multi-stage polymer relative to only the solids portion in the resulting mixture is at least 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight, advantageously at least 50% by weight.

The amount of the aqueous dispersion of the (meth)acrylic polymer (P1) and the aqueous dispersion of the multi-stage polymer is such that the weight proportion of the multi-stage polymer to only the solid portion in the resulting mixture is at most 99% by weight, preferably It is selected in such a way that it is at most 95% by weight, more preferably at most 90% by weight.

The amounts of the aqueous dispersion of the (meth)acrylic polymer (P1) and the aqueous dispersion of the multi-stage polymer are such that the weight percentage of the multi-stage polymer relative to only the solid portion in the resulting mixture is 5% to 99% by weight, It is preferably selected in a manner of 10%-95% by weight, more preferably 20%-90% by weight.

The recovery step b) of the process for producing the polymer composition according to the invention is preferably carried out by coagulation or spray drying.

A method of manufacturing a polymer composition according to the invention can optionally comprise an additional step c) of drying the polymer composition.

Dry means that the polymer composition according to the invention contains less than 3% by weight of moisture, preferably less than 1.5% by weight of moisture, more preferably less than 1.2% by weight of moisture.

Moisture can be measured by a thermobalance, which heats the polymer composition and measures the weight loss.

The method of making the polymer composition according to the invention preferably yields a polymer powder. The polymer powder of the invention is in the form of particles. Polymer powder particles include agglomerated primary polymer particles made by a multi-step process and a (meth)acrylic polymer (P1).

For the polymer powders of the invention, it has a volume median particle size D50 of 1 μm-500 μm. Preferably, the volume median particle size of the polymer powder is 10 μm-400 μm, more preferably 15 μm-350 μm, advantageously 20 μm-300 μm.

The D10 of the particle size distribution by volume is at least 7 μm, preferably 10 μm.

The D90 of the particle size distribution by volume is at most 950 μm, preferably at most 500 μm, more preferably at most 400 μm.

The invention also relates to the use of the polymer composition according to the invention in the form of a polymer powder as a masterbatch for thermosetting or thermoplastic polymers.

Masterbatches are mixed with other resins or polymers. The proportion of masterbatch used is at most 90% by weight, based on the thermoset or thermoplastic polymer and the composition containing the polymer composition according to the invention. The proportion of masterbatch used is at least 10% by weight, based on the thermoset or thermoplastic polymer and the composition containing the polymer composition according to the invention.

An additional aspect of the invention relates to an impact modified polymer composition.

With respect to the impact modified polymer composition according to the invention,
a) a polymer (P2); and b) a (meth)acrylic polymer (P1); and c) a multi-stage polymer, characterized in that the multi-stage polymer constitutes at least 5% by weight of the composition.

Preferably, the impact-modified polymer composition according to the invention comprises
a) a polymer (P2), and b) a (meth)acrylic polymer (P1), and c) a polymer obtained by a multi-stage process,
- one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C,
- one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C
wherein the multi-stage polymer comprises at least 5% by weight of the composition.

The multistage polymer and (meth)acrylic polymer (P1) are the same as defined above.

Each stage (A) and (B) comprising polymers (A1) and (B1), respectively, and the properties of each polymer (A1) and (B1) are the same as defined above.

As regards the polymer (P2), according to the invention it is a thermosetting resin R1 or a thermoplastic polymer.

The thermosetting resin R1 is preferably selected from epoxy, polyester or (meth)acrylic resins.

As regards epoxy resins, according to the invention, it can be any organic compound having at least two oxirane-type functional groups that can be polymerized by ring opening.

These epoxy resins (abbreviated as E1) can be monomeric or polymeric on the one hand and aliphatic, cycloaliphatic, heterocyclic or aromatic on the other hand. Examples of such epoxy resins include resorcinol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl-p-amino-phenol, bromobisphenol F diglycidyl ether, triglycidyl ether of m-amino-phenol, tetraglycidylmethylene dianiline, Mention may be made of the triglycidyl ether of (trihydroxy-phenyl)methane, the polyglycidyl ether of phenol-formaldehyde novolak, the poly-glycidyl ether of ortho-cresol novolak, and the tetraglycidyl ether of tetraphenyl-ethane. Mixtures of at least two of these resins can also be used.

In a first more preferred embodiment,
a) an epoxy resin E1 having a Tg of 25° C. or less, and b) a (meth)acrylic polymer (P1) containing 80%-100% by weight of methyl methacrylate, and c) a polymer obtained by a multi-stage process. hand,
- one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C,
- one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C,
characterized in that the multi-stage polymer comprises at least 5% by weight of the composition.

In a second more preferred embodiment,
a) an epoxy resin E1, and b) a (meth)acrylic polymer (P1) containing a functional comonomer, and c) a polymer obtained by a multi-step process,
- one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C,
- one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C,
The impact modified polymer composition according to the present invention comprising a polymer comprising a is characterized in that the multi-stage polymer constitutes at least 5% by weight of the composition.

Preferably, the epoxy resin E1 is resorcinol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl-p-amino-phenol, bromobisphenol F diglycidyl ether, triglycidyl ether of m-amino-phenol, tetraglycidylmethylenedianiline , triglycidyl ether of (trihydroxy-phenyl)methane, polyglycidyl ether of phenol-formaldehyde novolac, poly-glycidyl ether of ortho-cresol novolac, and tetraglycidyl ether of tetraphenyl-ethane.

The impact modified polymer composition according to the invention contains 1%-90% polymer obtained by a multi-stage process.

With respect to the method of making the impact modified polymer composition according to the present invention,
a) mixing epoxy resin E1 with a masterbatch, said masterbatch being a polymer composition comprising a (meth)acrylic polymer (P1) and a multistage polymer.

The multistage polymer and (meth)acrylic polymer (P1) are the same as defined above.

Epoxy resin containing polymer compositions can be cured.

In a third more preferred embodiment,
a) a methacrylic resin, and b) a (meth)acrylic polymer (P1) containing 80%-100% by weight of methyl methacrylate, and c) a polymer obtained by a multi-step process,
- one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C,
- one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C
characterized in that the multi-stage polymer comprises at least 5% by weight of the composition.

The impact modified polymer composition containing the methacrylic resin is preferably an adhesive composition.

[Evaluation method]
AFM Atomic Force Microscopy (AFM) is performed on a VEECO D3100 in tapping mode. Two modes are used to acquire the images, the height mode to obtain the topography of the surface and the phase contrast mode to obtain the viscoelastic properties.

The sample is cooled to -90°C and cut by microtome to break the sample for AFM and to obtain a thin, virtually smooth surface. The cut sample slices have a thickness of about 100 nm.

Molecular Weight: The weight average molecular weight (Mw) of a polymer is determined by size exclusion chromatography (SEC).

The glass transition (Tg) of a polymer is measured by equipment capable of performing thermomechanical analysis. RDAII "RHEOMETRICS DYNAMIC ANALYSER" proposed by Rheometrics Company was used. Thermomechanical analysis accurately measures the viscoelastic change of a sample in response to applied temperature, strain or deformation. The frequency used is 1 Hz. The instrument continuously records the deformation of the sample during a program of controlled temperature changes while the dye remains fixed. Results are obtained by showing the elastic modulus (G'), loss factor and tan delta as a function of temperature. When the derived tan δ is equal to zero, the Tg will be higher than the temperature read on the tan δ curve.

Particle size analysis: The particle size of primary particles after multi-stage polymerization is measured by Zetasizer Nano S90 manufactured by MALVERN. The particle size of the polymer powder is measured with a Malvern Mastersizer 3000 manufactured by MALVERN. A Malvern Mastersizer 3000 instrument equipped with a 300 mm lens measuring the range 0.5-880 μm is used for the evaluation of weight average powder particle size, particle size distribution and percent fines.

Comparative example 1
Synthesis of Multistage Polymers (Core Shell Particles) 1st Stage - Polymerization of the Core: In a 20 liter high pressure reactor, 116.5 parts of deionized water, 0.1 part of potassium salt of tallow fatty acid as an emulsifier, 1,3- 21.9 parts butadiene (BD), 0.1 parts t-dodecyl mercaptan, and 0.1 parts p20 methane hydroperoxide were charged as initial kettle charges. The solution was heated with stirring to 43° C., at which point the redox catalyst solution (4.5 parts water, 0.3 parts sodium tetrapyrophosphate, 0.004 parts iron sulfate and 0.3 parts glucose) was charged. , effectively initiated the polymerization. The solution was then further heated to 56° C. and held at this temperature for 3 hours. 3 hours after the start of polymerization, the second monomer (77.8 parts BD, 0.2 parts t-dodecyl mercaptan) was charged, additional emulsifier and reducing agent (30.4 parts deionized water, emulsifier tallow fatty acid Potassium salt of (2.8 parts, 0.5 parts dextrose), as well as additional initiator (0.8 parts p-menthane hydroperoxide) were added continuously over 8 hours. Following completion of the second monomer addition, the remaining emulsifier and reducing agent charges plus initiator were added continuously over an additional 5 hours. Thirteen hours after the initiation of polymerization, the solution was heated to 68° C. and allowed to react until at least 20 hours had passed since the initiation of polymerization to produce polybutadiene rubber latex R1. The resulting polybutadiene rubber latex (R1) contained 38% solids and had a weight average particle size of about 160 nm.

Second Stage - Shell 1 (Outer Shell) Polymerization: In a 3.9 liter reactor, 75.0 parts polybutadiene rubber latex R1, 37.6 parts deionized water, and 0.1 parts on a solids basis. of sodium formaldehyde sulfoxylate. The solution was stirred, purged with nitrogen and heated to 77°C. Once the solution reaches 77° C., a mixture of 22.6 parts methyl methacrylate, 1.4 parts divinylbenzene and 0.1 parts t-butyl hydroperoxide initiator is added continuously over 70 minutes, It was then held for 80 minutes. Thirty minutes after the start of the hold time, 0.1 part sodium formaldehyde sulfoxylate and 0.1 part t-butyl hydroperoxide were added to the reactor all at once. Following a hold time of 80 minutes, the stabilizing emulsion was added to the graft copolymer latex. 3.2 parts deionized water (based on graft copolymer weight), 0.1 parts oleic acid, 0.1 parts potassium hydroxide, and 0.9 parts 3-(3,5-di-tert A stabilized emulsion was prepared by mixing octadecyl-butyl-4-hydroxyphenyl)propionate. The resulting core-shell latex (multistage polymer MP1) had a weight average particle size of about 180 nm and a solids content of 38%.

Coagulation: A jacketed 3 L vessel equipped with a stirrer is continuously charged with 500 g of a latex of core-shell particles (multistage polymer MP1) with a solids content of 14.1%. Under stirring at 300 r/min, the solution temperature is raised to 52°C, then 1.6% sulfuric acid aqueous solution is injected to obtain a coagulated material heat-treated at 96°C. The pH was adjusted to 2-6 with NaOH during coagulation. The coagulated material was subsequently screened in a centrifuge and washed with deionized water. After screening and drying, a powder with less than 1% residual volatiles is obtained.

This powder (20% proportion) is dissolved in DGEBA epoxy resin at ambient temperature. The hardener component (Jeffamine) was then added, mixed (so that the final resin had 10% solidified material) and cured at 120°C for 2 hours.

The dispersion of the additive was observed with an AFM device, and the dispersion was not good, and aggregates of particles could be observed (see AFM photograph in FIG. 1).

Example 1:
A multistage polymer MP1 is prepared in the same manner as in Comparative Example 1.

Synthesis of copolymer P1: Semi-continuous process: 1700 g deionized water, 0.01 g FeSO4 and 0.032 g ethylenediaminetetraacetic acid, sodium salt (dissolved in 10 g deionized water), 3 dissolved in 110 g deionized water .15 g sodium formaldehyde sulfoxylate and 21.33 g emulsifier potassium salt of tallow fatty acid (dissolved in 139.44 g water) are charged to the reactor with stirring and the mixture is stirred until completely dissolved. bottom. Three successive vacuum-nitrogen purges were performed to place the reactor under a slight vacuum. The reactor was then heated. At the same time, a mixture containing 960.03 g methyl methacrylate, 106.67 g dimethylacrylamide and 10.67 g n-octyl mercaptan was nitrogen-degassed for 30 minutes. The reactor was heated at 63°C and maintained at this temperature. The monomer mixture was then introduced into the reactor at 180 minutes using a pump. In parallel, 5.33 g of tert-butyl hydroperoxide solution (dissolved in 100 g of deionized water) are introduced (same addition time). The lines were rinsed with 50g and 20g of water. The reaction mixture was then heated at a temperature of 80° C. and the polymerization was completed 60 minutes after the end of the monomer addition. The reactor was cooled to 30°C. The solids content obtained is 34.2%. The weight average molecular weight of copolymer P1 is M _w =28000 g/mol.

Coagulation: A mixture of 139.14 g of multistage polymer MP1 latex and 51.54 g of copolymer P1 latex is diluted with 309.32 g of deionized water to give 500 g of latex mixture with 14.1% solids content. Place 500 g of the prepared mixture latex in a jacketed 3 L vessel equipped with a stirrer. Under stirring at 300 r/min, the solution temperature is raised to 52°C, then 1.6% sulfuric acid aqueous solution is injected to obtain a coagulated material heat-treated at 96°C. The pH was adjusted to 2-6 with NaOH during coagulation. The coagulated material was subsequently screened in a centrifuge and washed with deionized water. After screening and drying, a powder with less than 1% residual volatiles is obtained.

This powder (20% proportion) is dissolved in DGEBA epoxy resin at ambient temperature. The hardener component (Jeffamine) was then added, mixed (so that the final resin had 10% solidified material) and cured at 120°C for 2 hours.

When the dispersion of the additive is observed by AFM equipment, the dispersion is very good and well-dispersed particles can be observed. See photo.

Claims (18)

a (meth)acrylic polymer (P1) having a weight average molecular weight Mw of less than 80 000 g/mol,
a) one layer (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C, and b) one layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C.
wherein the multilayer polymer constitutes at least 40% and at most 90% by weight of the polymer composition, polymer (A1) comprising at least 50% by weight of polymer units derived from isoprene or butadiene, A polymer composition , wherein the polymer (B1) is an acrylic or methacrylic polymer . a (meth)acrylic polymer (P1) having a weight average molecular weight Mw of less than 80000 g/mol,
a) one layer (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C, and b) one layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C.
wherein the multilayer polymer constitutes at least 40% by weight and at most 90% by weight of the polymer composition, polymer (A1) is a silicone rubber-based polymer, and polymer (B1) is acrylic or A polymer composition that is a methacrylic polymer . Polymer composition according to claim 1 or 2 , characterized in that the (meth)acrylic polymer (P1) has a weight-average molecular weight Mw of less than 70000 g/mol. From claim 1, characterized in that layer (A) is the first layer and layer (B) comprising polymer (B1) is grafted onto layer (A) comprising polymer (A1). 4. The polymer composition according to any one of 3 . The (meth)acrylic polymer (P1) contains (meth)acrylic monomers constituting 50% by weight or more of the (meth)acrylic polymer (P1), more preferably the (meth)acrylic polymer (P1) is at least 60% by weight. %, advantageously at least 70% by weight, of ( meth )acrylic monomers. Polymer composition according to any one of claims 1 to 5 , characterized in that the (meth)acrylic polymer (P1) also comprises a functional comonomer. a) mixing the (meth)acrylic polymer (P1) with the multilayer polymer,
b) recovering the mixture obtained in the previous step in the form of a polymer powder, the (meth)acrylic polymer (P1) and the multilayer polymer in step a) being in the form of a dispersion in the aqueous phase, 7. A method of making a polymer composition according to any one of claims 1-6 . Use of the polymer composition according to any one of claims 1 to 6 or obtainable by the process according to claim 7 as a masterbatch in thermosetting or thermoplastic polymers. Use of the polymer composition according to any one of claims 1 to 6 or obtainable by the process according to claim 7 as a masterbatch in a thermosetting resin, the resin being epoxy, polyester or (Meth)acrylic resins used. Use according to claim 9 , characterized in that the thermosetting resin is an epoxy resin. a) a polymer (P2), and b) a (meth)acrylic polymer (P1) having a weight average molecular weight Mw of less than 80 000 g/mol, and c) a polymer obtained by a multi- stage process,
- one layer (A) comprising a polymer (A1) with a glass transition temperature below 0°C,
- one layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C
wherein the multi-layered polymer constitutes at least 5% by weight of the impact-modified polymer composition and the multi-layered polymer comprises only b) and c) comprising at least 40% and at most 90% by weight of the polymer (A1) comprising at least 50% by weight of polymer units derived from isoprene or butadiene, and polymer (B1) being an acrylic or methacrylic polymer An impact modified polymer composition. a) a polymer (P2), and b) a (meth)acrylic polymer (P1) having a weight average molecular weight Mw of less than 80 000 g/mol, and c) a polymer obtained by a multi- stage process,
- one layer (A) comprising a polymer (A1) with a glass transition temperature below 0°C,
- one layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C
wherein the multi-layered polymer constitutes at least 5% by weight of the impact-modified polymer composition and the multi-layered polymer comprises only b) and c) at least 40% by weight and at most 90% by weight of the impact-modified polymer, characterized in that the polymer (A1) is a silicone rubber-based polymer and the polymer (B1) is an acrylic or methacrylic polymer Composition. 13. Impact-modified polymer composition according to claim 11 or 12 , characterized in that the (meth)acrylic polymer (P1) has a weight-average molecular weight Mw of less than 70000 g/mol. 14. Impact resistant according to any one of claims 11 to 13 , characterized in that the polymer (P2) is a thermosetting resin R1, preferably chosen from epoxy, polyester or (meth)acrylic resins. Improved polymer composition. The polymer (P2) is a thermosetting resin R1 which is an epoxy resin E1 having a Tg of 25° C. or less, and the (meth)acrylic polymer (P1) contains 80%-100% by weight of methyl methacrylate. 14. An impact-modified polymer composition according to any one of claims 11 to 13 , characterized in that. 14. Polymer (P2) according to any one of claims 11 to 13 , characterized in that the polymer (P2) is a thermosetting resin R1 which is an epoxy resin E1, and the (meth)acrylic polymer (P1) comprises a functional comonomer. The impact modified polymer composition described. 14. The polymer (P2) according to any one of claims 11 to 13 , characterized in that the polymer (P2) is a methacrylic resin and the (meth)acrylic polymer (P1) contains 80%-100% by weight of methyl methacrylate. The impact modified polymer composition described. a) A process for producing an impact modified polymer composition comprising the step of mixing epoxy resin E1 with a masterbatch, wherein said masterbatch is the A method comprising a polymer composition obtainable by the method described in 1.

Images